CN105251440B - The preparation and application of a kind of refinery decolorization agent and cleaning for edible oil - Google Patents
The preparation and application of a kind of refinery decolorization agent and cleaning for edible oil Download PDFInfo
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Abstract
Preparation and application that a kind of refinery decolorization agent for edible oil is cleaned.By chlorate aqueous solution under conditions of inorganic acid or organic acid make reductant-oxidant, combined available chlorine gas is made, adsorbed again through stablizing agent carrier hydroxide and the secondary chemical reaction of silicon compound, then obtain graininess composite finished product refinery decolorization agent by concentration, fluidized drying granulation.Especially acid reaction mother liquor does not make discharging of waste liquid, and byproduct sulfite is reclaimed after being reprocessed to waste liquid, then by reaction mother liquor reuse.The present invention can be used for animal and vegetable oil refinery decolorization, in particular for edible oil refinery decolorization, the sector can be made to make major contribution in terms of the energy-saving and emission-reduction that response country proposes, the present invention can make edible oil industry energy-saving more than 80%；Emission reduction oil-containing spent bleaching clay filter residue 100%.It can also be used for other food and organic matter decolourize.This technology product has great environmental protection, economic value, with wide popularizing application prospect；Occupy first place in the world.
Description
Technical field
The invention belongs to technical field of fine, it is related to a kind of preparation of new cleaning material-food processing aid
And application.
Background technology
China is edible oil consumption big country, national edible fat production total amount in 2014 45,210,000 tons (contain edible corn oil,
Tea oil, the small kind oil such as walnut oil, animal oil and secondary fine oil refining), and consumption figure, also in cumulative year after year, edible oil market is steady
Fixed advantage, foreign great You Qi groups also enter China one after another, to enjoy tax-exemption policies, are mostly set up factories in coastal area of china, only Tianjin
Large edible oil refinement enterprise of China and foreign countries three, Si Shijia are just entered in port, the edible fat production base as Largest In China.
Before this, it is domestic, edible oil industry is generally using adsorptivity atlapulgite (hereinafter referred to as carclazyte) to edible in the world
Oil refining is decolourized.With the development of science and technology, people's environmental consciousness is improved constantly, low-carbon environment-friendly energy-saving and emission-reduction are gradually rooted in the hearts of the people.
Carclazyte is had now found that as decolorizer of edible oil and there is many flaws, primary disadvantage is that substantial amounts of neutral oil has been adsorbed, according to enterprise
Industry is calculated, and absorption neutral oil is between 30~50% in the spent bleaching clay dregs of fat after filter, and the spent bleaching clay dregs of fat go out through twice pressing after filter
After black is containing glue oil, also containing 12~20% neutral oil in the spent bleaching clay dregs of fat, these spent bleaching clay dregs of fat are by regular factory
Family marries again Environment Protection Responsibility and is illegally sold to medium-sized and small enterprises, then after squeezing through three times and seeking profit, by oil-containing spent bleaching clay arbitrarily shed toward mountains and rivers,
Ditch ridge and in rainy season by punching toward rivers,lakes and seas, environmental pollution is extremely serious.Carclazyte is returned edible to the process for eating oil decolorization
Bad smell in oily pollution, to eliminate peculiar smell, adds 260 DEG C, 4~6h deodorization procedures, only this process consumption energy again
Account for oil enterprise always consumes energy more than 80%.Disclosed according to expert, carclazyte and deodorization procedures not only make oil product former fragrance,
The nutritions such as vitamin are eliminated totally, return and a certain amount of acrylic acid, acrylamide, Benzpyrene etc. are added in edible oil
Carcinogenic substance.
In recent years, the haze weather of Beijing-Tianjin area, the coastal red algae taken place frequently, blue-green algae and giving up that coastal numerous oily factory discharges
Water, boiler waste gas, deodorization waste gas, waste coal slag, the spent bleaching clay dregs of fat discharge it is inseparable.
With the development of science and technology, people gradually recognize shortcoming and the harm of carclazyte, and urgent need has a kind of cleaning material
To replace carclazyte.The present inventor contemplates some existing materials of market first, by testing one by one it was found that it is in grease
On percent of decolourization all do not reach the regulation of national standard, and process equipment requires cumbersome, least it is acceptable be these materials with
Seriously oxidized grease during grease reacts.
The content of the invention
The present invention seeks to solve blemishes that processing aid carclazyte used in existing edible fat production industry is present there is provided
A kind of production method of cleaning material-refinery decolorization agent of substitution carclazyte and application.So-called cleaning is embodied in two aspects：
One is the production process cleaning of product of the present invention, without slag and effluent discharge；Two be products application process cleans of the present invention, is not also had
There is slag and effluent discharge.
Present invention firstly provides the clean method for preparing of the refinery decolorization agent for edible oil, this method is by chloric acid salt solution
Solution is made in inorganic acid or organic acid under conditions of reductant-oxidant, and combined available chlorine gas is made, then through stablizing agent carrier hydrogen
Oxide and silicon compound it is secondary chemical reaction absorption, then by concentration, fluidized drying granulation obtain graininess composite finished product-
Refinery decolorization agent, specifically includes following steps：
1st, the preparation of combined available chlorine monomer；
To be 0.01~1 in mass ratio：The sodium chloride and sodium chlorate that 1 processing compound is calculated add material-compound tank, stirring
Mixed aqueous solution A is dissolved as, mixed aqueous solution A total concentrations are 100g/L~800g/L, add retort standby；
Described sodium chloride and the mass ratio of sodium chlorate are preferably 0.06~0.1：1；Mixed aqueous solution A total concentrations are preferably
300g/L~700g/L；
Described sodium chloride and sodium chlorate can be used to lower chloride and replace：Chlorine, liquid chlorine, sodium chlorate, potassium chlorate, sodium chloride
In one or more；
2nd, the preparation of absorption carrier complexing agent；
It is 5~50 in mass ratio by the sodium hydroxide and calcium hydroxide and water of content 96%：5~10：100 in material-compound tank
Mixed aqueous solution B is made into, normal temperature is standby；The mass ratio of described sodium hydroxide, calcium hydroxide and water is preferably 5~30：10：
100；More preferably 28：10：100；
Wherein calcium hydroxide refers to：Calcium hydroxide and water are stirred into milk of lime after precipitation, take supernatant to use, its hydrogen
The mass ratio of calcium oxide and water is：40：100；
Described calcium hydroxide and sodium hydroxide can select one or more of and replace：Calcium hydroxide, sodium hydroxide, hydrogen
Potassium oxide, potassium carbonate, sodium carbonate；
3rd, the preparation of combined available chlorine mixed gas；
Under conditions of retort ventilation, inorganic acid or organic acid are added into the mixing water that the 1st step is prepared by technological requirement
Make redox reaction in solution A, generate combined available chlorine mixed gas, the combined available chlorine gas includes ClO2、H2、O2With
HCl；
Described inorganic acid or organic acid are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, tartaric acid, lactic acid, apple
One or several kinds in tartaric acid or boric acid；Described acid preferably hydrochloric acid；
4th, wash；
The combined available chlorine mixed gas that 3rd step is generated is firstly introduced into scrubbing tower, the mixed aqueous solution prepared with the 1st step
A is washed as cleaning solution, to remove hydrochloric acid；
5th, adsorb；
Combined available chlorine gas after washing is introduced into adsorption tower, adsorption liquid is used as using the mixed aqueous solution B that the 2nd step is prepared
Carry out secondary chemical reactive synthesis, when combined available chlorine gas content reaches 20%~26%, sodium hydrate content 1%~
When 3%, chemical reaction is completed, in time discharging；
6th, the sodium metasilicate of modulus 24 and above-mentioned 5th step chemical reaction liquid are added into 1 ㎏ by every 10% combined available chlorine gas
Proportioning, the 40r/min mixing 20min under the conditions of 60 DEG C obtains the fluid product of refinery decolorization agent；
7th, the refinery decolorization agent fluid product obtained the 6th step is concentrated under 80 DEG C, -0.098mpa vacuum conditions
After solid content 50%, then through bed spray it is dry granular solid product, product water content≤5%, effective chlorine gas contains
The solid product of refinery decolorization agent is made 75%~80% in amount control.
Solid refinery decolorization agent for edible oil prepared by the method for the invention, its constituent and content such as table 1
It show：
Table 1, solid refinery decolorization agent composition and content table
Liquid purification decolorising agent for edible oil prepared by the method for the invention, its constituent and content such as table 2
It show：
Table 2, liquid purification decolorising agent composition and content table
Refinery decolorization agent of the present invention for edible oil can be used for animals and plants refining raw food oil, and substitution carclazyte is dynamic plant
Thing edible oil refinery decolorization.The refinery decolorization agent is that the method for edible oil decolorization is as follows：
Food plant crude oil to be decolourized is added in the bleacher of former technique and is warming up to 60 DEG C~80 DEG C, in the bar of stirring
The aqueous solution of solid refinery decolorization agent preparation prepared by the above method is added under part, addition is using the agent of solid refinery decolorization as oil weight
0.1%~0.5%；
In the aqueous solution of the solid refinery decolorization agent of addition, the proportioning of water and solid refinery decolorization agent is 4：0.1~0.5；
Kept for 60 DEG C~80 DEG C, 30min~40min is reacted under conditions of stirring, terminate to decolourize.
Described solid refinery decolorization agent can be replaced with liquid purification decolorising agent, and the usage amount of liquid purification decolorising agent is
Three times of solid refinery decolorization agent quality.
Refinery decolorization agent prepared by the present invention is to be added with chlorate on the basis of inorganic acid and organic acid oxidation reduction
The NEW TYPE OF COMPOSITE product of corresponding functional component chemical synthesis, be mainly manifested in it is following some：
Firstth, the redox to chlorate can be participated in respectively by adding the species of a variety of inorganic acids or organic acid
Journey, available for the present invention acid can be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, tartaric acid, lactic acid, malic acid,
One or several kinds in boric acid, the present invention preferably hydrochloric acid；Available for the present invention chloride can be chlorine, liquid chlorine, sodium chlorate,
One or more in potassium chlorate, sodium chloride, the present invention preferably sodium chlorate and sodium chloride.
Secondth, the secondary combination reaction that a variety of hydroxide participate in combined available chlorine is added, the present invention can select following
It is one or more：Calcium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, preferably calcium hydroxide and hydrogen-oxygen of the present invention
Change sodium.The compound composition of the wherein several functions feature such as sodium ion, calcium ion is formd with adsorbent, carrier and stabilizer
Effect, the technology finished product of making is more suitable for the purification and decoloration of animal and plant fat.
3rd, silicate component is added as the important composition of refinery decolorization agent prescription, and it can be made de- as effective chlorine
While color, bleaching, synergist, by other impurity flocculations, sedimentation in this product and grease, refinery decolorization agent is removed in oil
Residual.What it is available for the present invention can be silica, trichlorosilicane, silicon tetrachloride, trichlorosilane, silicone oil, sodium potassium silicate, silicon
Sour sodium, silicic acid, potassium silicate, sodium metasilicate, silane, cyclosilane one or more therein, the present invention preferably sodium metasilicate.Wherein dioxy
SiClx and sodium metasilicate are already applied to cleaning product, food, medicine and cosmetics.
Advantages and positive effects of the present invention：
The present invention is to add corresponding functional component on the basis of inorganic acid and organic acid oxidation reduction with chlorate
The NEW TYPE OF COMPOSITE product of chemical synthesis, has the following advantages that：
1st, the oxidation-reduction process to chlorate can be participated in respectively by adding the species of a variety of inorganic acids or organic acid；
2nd, the secondary combination reaction that a variety of hydroxide participate in combined available chlorine, wherein sodium ion, calcium ion etc. are added
The compound composition of several functions feature forms the effect with adsorbent, carrier and stabilizer, makes technology finished product more applicable
In the purification and decoloration of animal and plant fat；
3rd, silicate component is added as the important composition of refinery decolorization agent prescription, and it can be made de- as combined available chlorine
While color, bleaching, synergist, by other impurity flocculations, sedimentation in this product and grease, refinery decolorization agent is removed in oil
Residual；
The composition that product of the present invention adds element silicon is very beneficial for edible degumming of oil precipitation and decolourized, and works as refinery decolorization
When water-soluble silicon ion in agent is activated by the denaturant (acid) in oil refining process, cation replaces dissolution by hydrogen ion,
The hydroxyl group also dissolution therewith of silicon atomic core in silicon ion structure simultaneously, increases the molecular volume of silicon, spacing is lengthened, shape
Into micropore network specific surface area structure very big cellular material, this material is insoluble in oil and water, with powerful
Adsorption activity and decolorizing ability.Silicon ion not only adds the intensity of solid refinery decolorization agent particle in the accumulating phase, can also be in food
With playing a part of flocculated colloid in degumming of oil process and helping sedimentation, ultraviolet light screener is alternatively arranged as, prevents ultraviolet light from promoting
Product oxidation Decomposition of the present invention；Also as reducing agent, suppress the activity of effective chlorine molecule in Storage period, make transport safer,
Also shelf life of products is extended；
4th, with refinery decolorization agent made from the silicon calcium material of combined available chlorine combination adsorptivity to vegetable and animals oils and other foods
The organic matters such as product have superpower decolouring, deodorization, the function of impurity sedimentation；
5th, novel solid refinery decolorization agent available chlorine content of the present invention can reach 130ml/100mg, and the shelf-life is five
More than year, available chlorine content loss late≤1% is detected after 5 years；
6th, the application characteristic of refinery decolorization agent：Decolourized suitable for the strength refining of various animal and plant greases.Compared with carclazyte：
Refinery decolorization agent only needs the middle temperature of normal pressure to decolourize, (carclazyte needs highly energy-consuming high-temperature vacuum to decolourize)；Decolorization rate is fast；Consumption is few, only
It is the 5%~10% of carclazyte consumption；Labor strength diminishes；Reduce shipping storage expense；Workshop does not have black pollution；Nothing
Odor, is not required to oil product deodorization, only this item is that can save energy more than 80%；Entrained oil, does not refine yield rate high；Without waste oil filter residue
Discharge, oil enterprise waste oil filter residue emission reduction 100%；
7th, after with cleaning material refinery decolorization agent substitution carclazyte, oil enterprise energy-saving and emission-reduction amplitude is big, it will be apparent that reduce production
Cost adds benefit, is very environmentally friendly Novel clean material.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of the agent of edible oil refinery decolorization and cleaning.
Embodiment
With reference to embodiment, the present invention will be further described.The proportioning that the present invention includes but is not limited in following instance
Data and formula.
Embodiment 1：
1st, it is 0.3 according to mass ratio by sodium chloride and sodium chlorate：1 quality adds material-compound tank (1), and it is mixed to be dissolved in water
Heshui solution A, adjustment concentration is 300~600g/L, and 50 DEG C of heating makes it dissolve；Then the confined reaction tank (2) of ventilation is added
It is standby.
2nd, by the mol ratio 1.2 of hydrochloric acid and sodium chlorate：1 quality, hydrochloric acid metering infusion is entered the 1st step of ventilation
Retort (2) makees redox reaction；Redox reaction process material reaction equation in retort (2) is as follows：
NaCl+6NaCI+HCl+3H2O2+H2O=3O2+6Cl2+SO2+H2O。
3rd, regulate and control high pressure positive blower flow, coordinate the wind flow of supervisory instrument, online effective chlorine density display instrument data are adjusted
Hydrochloric acid solution addition is controlled, the ratio of the effective chlorine body of the mixing of air quantity and generation is reached 100：Between 0.1~50.
4th, the combined available chlorine mixed gas of generation is firstly introduced into scrubbing tower (10), made with the 1st step mixed aqueous solution A
Washed for cleaning solution, to remove hydrochloric acid.Increasing this inventive step can make to be free of in finished product or few hydrochloric, save hydrogen-oxygen
Change the consumption of sodium.
5th, the combined available chlorine gas after washing is introduced into adsorption tower (4) to carry out using mixed aqueous solution B as adsorption liquid
Secondary chemical reactive synthesis.
Adsorption tower is made up of with mixed aqueous solution B the sodium hydroxide and calcium hydroxide and water of mass content 96%, and it is matched
Quality is 10~28：10：100.60 DEG C~80 DEG C use.Wherein calcium hydroxide refers to：Calcium hydroxide and water are stirred into lime
Breast after precipitation, takes supernatant to use, the mass ratio of its calcium hydroxide and water：40：100；
Absorb process：Absorbing reaction formula of the combined available chlorine in adsorption tower (4) is as follows：
NaOH+Cl2+Ca(OH)2+H2O+O2=NaOH+Cl2+Ca(OH)2+H2O
6th, adsorption liquid is taken to detect at any time, it is once-combined effectively every 20min~30min sampling detections during system operation
The content of chlorine and sodium hydroxide, when available chlorine content reaches 20%~26%；Sodium hydrate content is at 1.%~3%, chemistry
Reaction is completed.Discharging in time.
The 7th, the sodium metasilicate of modulus 24 and above-mentioned 6th step chemical reaction liquid are added to 1 ㎏ proportioning by every 10% effective chlorine,
Under the conditions of 60 DEG C, 40r/min mixing 20min obtain the fluid product of refinery decolorization agent.Its chemical molecular formula：
NaOH·Cl2·Ca(OH)2·Na2SiO3·H2O
8th, by the fluid product of above-mentioned refinery decolorization agent in being concentrated into solid content under 80 DEG C, -0.098mpa vacuum conditions
After 50% or so, then through bed spray it is dry granular solid product, product water content≤5%, combined available chlorine content
130mL/100g is reached as high as, combined available chlorine control for safety reasons obtains the solid production of refinery decolorization agent 75%~80%
Product.
Its chemical molecular formula：
NaOH·Cl2·H2·Ca(OH)2·Na2SiO3。
9th, tail gas recycle
The tail gas adsorbed through absorption tower (4) enters recovery tower again, and it is compound to the residual in tail gas effective to make adsorbent with water
Chlorine is reclaimed, and then tail gas is emptied.40%~50% effective chlorine can be still stored up in recovered liquid, the dissolving available for sodium chlorate
Use water.This increased program is conducive to the environment protection clean of vent gas, is conducive to reclaiming product, reduces material consumption.
Above-mentioned whole chemical reaction is carried out all under conditions of closing, and preparation technology flow is referring to Fig. 1.
Embodiment 2, waste reaction solution recycle
The production process of refinery decolorization agent, finished product (dry product) per ton about produces 2.7 cubes of waste reaction solutions, through assay
Content of hydrochloric acid 23%~27% in waste liquid, saltcake mixture content 30%~50%.What effluent purifying reuse of the present invention was taken
Technical scheme comprises the following steps：
1), waste liquid injection professional ripe can be refined to the vacuum concentration pot operated, the concentrated sulfuric acid is then added, the concentrated sulfuric acid is with giving up
Liquid by volume 0.005：1 adds.At 50 DEG C~200 DEG C, preferably 80 DEG C~120 DEG C progress vacuum evaporations work as evaporation capacity
When reaching waste liquid total amount 40%, terminate concentration；
2) above-mentioned 1) step concentrate, is injected into crystallisation by cooling groove, stirred with 1r/min speed, regulating and controlling temperature is 0 DEG C~5
DEG C, it is molded about 1h, the clear wash rice of mother liquor to crystal grain.
3) above-mentioned crystallized stock, is transferred to link-suspended basket centrifuge, 1200r~1500r is carried out and centrifuges, obtain ten water sulfuric acid
Sodium solid phase and diluted acid mother liquor liquid phase.
4), above-mentioned sal glauberi enters vacuum drier drying, 100 DEG C~200 DEG C of temperature control.Anhydrous sodium sulfate is obtained, it is every
Index proves that product meets commercial standard by detecting.
5), above-mentioned diluted acid mother liquor, which is returned, prepares mixed aqueous solution A for preparing after the 1st successive step acidity in embodiment 1
Combined available chlorine monomer is used.
Due to containing the semi-finished product in a certain amount of combined available chlorine and reaction in reaction mother liquor, applied to lower batch materials
React again, serve initiation catalytic action, it is relatively more first batch of to improve 9% with proportioning, with the product earning rate of condition.
Embodiment 3
The sodium chlorate and the sodium chloride of content 98% of content 99% are taken by 1：0.06 mass ratio mixing, 350g/L is made into water
Concentration add dosage bunker, after dissolving under conditions of 40r/min, 50 DEG C, add retort；Start high pressure positive blower, initial wind
Amount is temporarily adjusted to 908m3/h.Then 10mol/L hydrochloric acid solution is slowly added into retort with measuring pump, now in the oxygen of hydrochloric acid
Change the lower sodium chloride of reduction and be converted to Cl2, sodium chlorate discharges ClO2Gas, now has ClO in retort2、Cl2、H2、O2, it is a variety of
Gaseous mixture, the present invention is collectively referred to as combined available chlorine.Combined available chlorine presses 0.1~50 with air stream：100 volume ratio is in time
Discharge retort.The available chlorine content in retort is nearly monitored by effective chlorine on-line measurement instrument simultaneously；When in retort
When available chlorine content is too high, then to increase ventilation in time, or reduce the ration of hydrochloric acid solution；When effective chlorine in retort
When content is too low, then to reduce ventilation in time, or increase the ration of hydrochloric acid solution.Control ventilation and available chlorine
Volume ratio 100m3：0.1m3~50m3Stable operation.
The sodium hydroxide, calcium hydroxide and water of content >=96% are pressed 28.5:10:100 mass ratio is stirred in dosage bunker
Dissolving clarification is mixed, wherein calcium hydroxide uses clarification limewash.Then added from absorption top of tower circulation；The discharge of autoreaction tank
Gaseous mixture enters from closed pipeline from absorption tower bottom, is inhaled in Ta Nei with sodium hydroxide, the secondary chemical reaction of calcium hydroxide
Attached, residual air is discharged from top of tower, then after recover makees compound composition recovery of the adsorbent to residual with water, residual air row
It is empty；
Therebetween every 20min~30min sample examinations once, the content of detection combined available chlorine and sodium hydroxide, when multiple
Close available chlorine content and reach (in terms of chlorine) 20Cl~26Cl/100ml, sodium hydrate content is at 0.5%~0.8%, and chemistry is anti-
It should complete.Discharging in time.
The sodium metasilicate of modulus 24 and above-mentioned chemical reaction liquid are added to 1 ㎏ proportioning by every 10% effective chlorine, in 50 DEG C of conditions
Lower 40r/min mixing 20min.This is the fluid product of refinery decolorization agent.
By refinery decolorization agent fluid product derived above in being concentrated into solid content under 80 DEG C, -0.098mpa vacuum conditions
After 50%, then through bed spray it is dry granular solid product, product water content≤5%, available chlorine content control exist
75%~80%, the solid product of refinery decolorization agent is made.
Embodiment 4
Take the sodium chlorate and the sodium chloride 1 of content 98% of content 99%：0.06 mass ratio mixing, is made into 350g/L's with water
Concentration adds dosage bunker, after being dissolved under conditions of 40r/min, 50 DEG C, adds retort；Start high pressure positive blower, initial air quantity
Temporarily it is adjusted to 908m3/h.Then 10mol/L hydrochloric acid solution is slowly added into retort with measuring pump, now in the oxidation of hydrochloric acid
The lower sodium chloride of reduction is converted to Cl2, sodium chlorate discharges ClO2.Now there is ClO in retort2、Cl2、H2、O2, a variety of gaseous mixtures,
The present invention is collectively referred to as combined available chlorine.Combined available chlorine presses 0.1m with air stream3~50m3：100m3Volume ratio arrange in time
Go out retort.The combined available chlorine content in retort is nearly monitored by on-line measurement instrument simultaneously；When compound in retort
When available chlorine content is too high, then to increase ventilation in time, or reduce the ration of hydrochloric acid solution；When effective chlorine in retort
When content is too low, then to reduce ventilation in time, or increase the ration of hydrochloric acid solution.Control ventilation and available chlorine
Volume ratio 100m3：0.1m3~50m3Stable operation.
The sodium hydroxide, calcium hydroxide and water of content >=96% are pressed 28.5:10:100 mass ratio is stirred in dosage bunker
Dissolving clarification is mixed, wherein calcium hydroxide uses clarification limewash.Then added from absorption top of tower circulation；The discharge of autoreaction tank
Gaseous mixture is entered by closed pipeline from absorption tower bottom, is inhaled in Ta Nei with sodium hydroxide, the secondary chemical reaction of calcium hydroxide
Attached, residual air is discharged from top of tower, then after recover makees compound composition recovery of the adsorbent to residual with water, residual air row
It is empty；
Therebetween every 20min~30min sample examinations once, the content of detection combined available chlorine and sodium hydroxide, when multiple
Close available chlorine content and reach (in terms of chlorine) 20Cl~26Cl/100ml, sodium hydrate content is at 0.5%~0.8%, and chemistry is anti-
It should complete.Discharging in time.
The sodium metasilicate of modulus 24 and above-mentioned chemical reaction liquid are added to 1 ㎏ proportioning by every 10% combined available chlorine, at 50 DEG C
Under the conditions of 40r/min mixing 20min.This is the fluid product of refinery decolorization agent.
By aforesaid liquid product in being concentrated under 80 DEG C, -0.098mpa vacuum conditions after solid content 50% or so, then pass through
Bed spray it is dry granular solid product, control product moisture content≤5%, combined available chlorine control 75ml~
80ml/100mg.This is the solid product of refinery decolorization agent.
Embodiment 5, the application of the refinery decolorization agent of the present invention for edible oil
Available for animals and plants refining raw food oil, substitution carclazyte is animals and plants edible oil refinery decolorization.The refinery decolorization agent
Method for edible oil decolorization is as follows：
Food plant crude oil to be decolourized is added in the bleacher of former technique and is warming up to 60 DEG C~80 DEG C, in the bar of stirring
The aqueous solution of solid refinery decolorization agent preparation prepared by claim 1 methods described is added under part, addition is refined de- with solid
Toner is the 0.1%~0.5% of oily weight；
In the aqueous solution of the solid refinery decolorization agent of addition, the proportioning of water and solid refinery decolorization agent is 4：0.1~0.5；
Kept for 60 DEG C~80 DEG C, 30min~40min is reacted under conditions of stirring, terminate to decolourize.
Solid refinery decolorization agent of the present invention can also be replaced with liquid purification decolorising agent, liquid purification decolorising agent
Usage amount is three times of solid refinery decolorization agent quality.
The edible oil decolourized in this manner can reach the color and luster of the national standard primary oil of related kind.
Claims (10)
1. the preparation method that a kind of refinery decolorization agent for edible oil is cleaned, it is characterised in that this method is water-soluble by chlorate
Liquid is made in inorganic acid or organic acid under conditions of reductant-oxidant, and combined available chlorine gas is made, then through stablizing agent carrier hydrogen-oxygen
Compound and the secondary chemical reaction absorption of silicon compound, then obtain graininess composite finished product essence by concentration, fluidized drying granulation
Decolorising agent processed, specifically includes following steps：
1st, the preparation of combined available chlorine monomer；
To be 0.01~1 in mass ratio：The sodium chloride and sodium chlorate that 1 processing compound is calculated add material-compound tank, stirring and dissolving
For mixed aqueous solution A, mixed aqueous solution A total concentrations are 100g/L~800g/L, add retort standby；
2nd, the preparation of absorption carrier complexing agent；
It is 5~50 in mass ratio by the sodium hydroxide and calcium hydroxide and water of content 96%：5~10：100 are made into material-compound tank
Mixed aqueous solution B, normal temperature is standby；
Wherein calcium hydroxide refers to：Calcium hydroxide and water are stirred into milk of lime after precipitation, take supernatant to use, its hydroxide
The mass ratio of calcium and water：40：100；
3rd, the preparation of combined available chlorine mixed gas；
Under conditions of retort ventilation, inorganic acid or organic acid are added into the mixed aqueous solution A that the 1st step is prepared by technological requirement
In make redox reaction, generate combined available chlorine mixed gas；The combined available chlorine gas includes ClO2、H2、O2And HCl；
4th, wash；
The combined available chlorine mixed gas that 3rd step is generated is firstly introduced into scrubbing tower, is made with mixed aqueous solution A prepared by the 1st step
Washed for cleaning solution, to remove hydrochloric acid；
5th, adsorb；
Combined available chlorine gas after washing is introduced into adsorption tower, carried out using the mixed aqueous solution B that the 2nd step is prepared as adsorption liquid
Secondary chemical reactive synthesis, when combined available chlorine gas content reaches 20%~26%, sodium hydrate content at 1%~3%,
Chemical reaction is completed, in time discharging；
6th, the sodium metasilicate of modulus 24 and above-mentioned 5th step chemical reaction liquid are added into matching somebody with somebody for 1 ㎏ by every 10% combined available chlorine gas
Than the 40r/min mixing 20min under the conditions of 60 DEG C obtains the fluid product of refinery decolorization agent；
7th, the refinery decolorization agent fluid product obtained the 6th step is in concentration under 80 DEG C~100 DEG C, -0.098mpa vacuum conditions
To solid content 50%, then through bed spray it is dry granular solid product, product water content≤5%, effective chlorine gas
The solid product of refinery decolorization agent is made 75%~80% in content control.
2. preparation method according to claim 1, it is characterised in that the quality of sodium chloride and sodium chlorate described in the 1st step
Than being preferably 0.06~0.1：1；Mixed aqueous solution A total concentrations are preferably 300g/L~700g/L.
3. preparation method according to claim 1, it is characterised in that sodium hydroxide, calcium hydroxide described in the 2nd step and
The mass ratio of water preferably 5~30：10：100.
4. preparation method according to claim 1, it is characterised in that inorganic acid or organic acid described in the 3rd step are salt
One or several kinds in acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, tartaric acid, lactic acid, malic acid or boric acid.
5. preparation method according to claim 4, it is characterised in that described acid preferably hydrochloric acid.
6. preparation method according to claim 1, it is characterised in that sodium chloride and sodium chlorate described in the 1st step can be used to down
Chloride is replaced：One or more in chlorine, liquid chlorine, sodium chlorate, potassium chlorate, sodium chloride.
7. the solid refinery decolorization agent for edible oil prepared by a kind of claim 1 methods described, it is characterised in that it is constituted
It is as shown in the table is for composition and content：
Solid refinery decolorization agent composition and content table
8. the liquid purification decolorising agent for edible oil prepared by a kind of claim 1 methods described, it is characterised in that it is constituted
It is as shown in the table is for composition and content：
Liquid purification decolorising agent composition and content table
9. the application of the refinery decolorization agent for edible oil prepared by a kind of claim 1 methods described, it is characterised in that be used for
Animals and plants refining raw food oil, substitution carclazyte is animals and plants edible oil refinery decolorization；The refinery decolorization agent is edible oil decolorization
Method is as follows：
Food plant crude oil to be decolourized is added in the bleacher of former technique and is warming up to 60 DEG C~80 DEG C, under conditions of stirring
The aqueous solution of solid refinery decolorization agent preparation prepared by claim 1 methods described is added, addition is with solid refinery decolorization agent
For the 0.1%~0.5% of oily weight；
In the aqueous solution of the solid refinery decolorization agent of addition, the proportioning of water and solid refinery decolorization agent is 4：0.1~0.5；
Kept for 60 DEG C~80 DEG C, 30min~40min is reacted under conditions of stirring, terminate to decolourize.
10. application according to claim 9, it is characterised in that described solid refinery decolorization agent liquid purification decolourizes
Agent is replaced, and the usage amount of liquid purification decolorising agent is three times of solid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510843789.1A CN105251440B (en) | 2015-11-26 | 2015-11-26 | The preparation and application of a kind of refinery decolorization agent and cleaning for edible oil |
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| CN201510843789.1A CN105251440B (en) | 2015-11-26 | 2015-11-26 | The preparation and application of a kind of refinery decolorization agent and cleaning for edible oil |
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| CN108130186A (en) * | 2016-12-01 | 2018-06-08 | 丰益(上海)生物技术研发中心有限公司 | A kind of discoloration method of grease |
| CN106635128A (en) * | 2016-12-27 | 2017-05-10 | 上海给力石油化工有限公司 | Solid compound flocculating decolorant for diesel oil and application method of solid compound flocculating decolorant |
| CN107033917A (en) * | 2017-04-21 | 2017-08-11 | 安徽家壹味食品有限公司 | A kind of agricultural use method of refining raw food oil waste liquid |
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| CN102952626B (en) * | 2012-11-06 | 2014-07-09 | 安徽新世界绿洲茶油有限公司 | Preparation process of cold-pressed tea seed oil |
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